Metallizable monoazo dyestuffs



Patented Oct. 23, 1951 METALLIZABLE MONOAZ O DYESTUFFS Hans Ruckstuhl,Otto Senn, and Walter Wehrli,

Basel, Switzerland, assignors to Sandoz A. G., Basel, Switzerland, aSwiss firm N Drawing. Application January 16, 1950, Se

rial No. 138,932. 1949 6 Claims.

The present invention relates to new metallizable monoazo dyestuffs andto the manufacture thereof.

It has been found according to the present invention that valuablemonoazo dyestuffs are obtained from diazotized phenylamides of 1-hydroxy 2 aminobenzene sulphonic acid, in which the phenylamidosulphonicacid group is in the 4-, 5- or 6-position, by coupling them with theamides of l-phenyl-5-pyrazolone-3-carboX ylic acid, in which onehydrogen atom of the carboxylic amide group can be replaced by methyl orethyl. If the carboxylic amide group in the dyestuff which is formed isunsubstituted then there may a methyl or methoxy group or a halogen atompresent in not more than one of the phenyl radicals.

As diazo components there can be used for example the followingcompounds:

The anilide of 1-hydroxy-2-aminobenzene-4- sulphonic acid, the anilideof l-hydroxy-2- aminobenzene-S-sulphonic acid, as well as thederivatives of these compounds substituted in the phenyl of thephenylamido group by at most one methylor methoxy group or one halogenatom and also 1-hydroxy-2-amino-4-chlorbenzene-5-sulphonic acid anilide,1-hydroXy-2- amino-l-chlorbenzene-6-sulphonic acid anilide, 1 hydroxy 2amino 4 methylbenzene 5 sulphonic acid anilide, l-hydroxy-Z-amino-4-methylbenzene 6 sulphonic acid anilide, 1- hydroxy 2 amino 6chlorbenzene 4 -sul phonic acid anilide, l-hydroxy-2-amino-6-methylbenzene-4-sulph0nic acid anidide.

As coupling components there can for example be used the amide of1-phenyl-5-pyrazolone-3- carboxylic acid, which can be substituted inthe phenyl radical by at most one methylor methoxy group or one halogenatom, or there can be used the methylor ethyl amide of l-pheny1-5-'pyrazolone-3-carboxylic acid.

The dyestuffs obtained according to the present process give by chromedyeing on wool deep yellowish-red to Bordeaux red shades. They areparticularly suitable for the neutral single bath chroming process. Theypossess excellent fastness to light with good fastness properties inother respects.

The following examples illustrate the invention without limiting it inany way. The parts are parts by weight.

Example 1 26.4 parts of 2-amino-1-hydroXybenzene-4- sulphonic acidanilide are indirectly diazotized in the usual manner with 6.9 parts ofsodium nitrite, and the diazo suspension is coupled with In SwitzerlandJanuary 21,

21 parts of 1-phenyl-5-pyrazolone-'3-carboxylic acid amide which isdissolved in parts. of

water with an excess of ammonia. After stirring for several hburs atill-15 0., the dyestuff which has precipitated is isolated. In the drystate the v dyestuff, which corresponds to the formula Ola OH?- 0:

is a brown-red powder which dissolves in 'concentrated sulphuric acidwith a yellow-orange color. stuff dissolves with a yellowish-red color.

Wool is dyed therewith yellowish-red by afterchroming or by the neutralmetachrome process.

The dyeings possess most outstanding fastness carbonizing and 1 tolight, very good fastness to good wet fastnesses.

Example 2 26.4 parts of 2-amino-1-hydroxybenzene-5- sulphonic acidanilide are indirectly diazotized in the usual way and the diazosuspension is coupled with 21 parts of 1-pheny1-5-pyrazolone-3-carboxylic acid amide which is dissolved in 100 parts of water with anexcess of ammonia. After stirring for several hours at 1015 C. the pre-5 cipitated dyestufl is isolated.

When dry the dyestuif, which corresponds to the formula is a brown-redpowder which dissolves in concentrated sulphuric acid with ayellowish-orange color. The dyestuff dissolves in dilute caustic sodasolution with a yellowish-red color.

f astnesses.

In dilute caustic soda solution the dy e- Example 3 29.8 parts of2-amino-4-chloro-l-hydroxybenzene-G-sulphonic acid anilide areindirectly diazotized the usualmanner with6 .9 partsl of sodium nitrite,and the diazo suspension is coupled with 21 parts of1-phenyl-5-pyrazolone-3 carboxylic acid amide which is dissolved in 100parts of water with an excess of; ammonia. After stirring for severalhours at IO-l? C., the dyestuif which has precipitated is isolated. In;the dry state the dyestuff is a brown-red powder which dissolves inconcentrated sulphuric acid and in dilute caustic soda solution with abrickred color. a r i Wool is dyed thereby bluish-red by afterchromingor by the neutral metachrome process.

The dyestuif corresponds to the formula Example 4 26.4 parts of2-amino-1Ehydroxybenzene-4- sulphonic acid anilide are indirectly diazotized in the usual manner with 6.9 parts of sodium nitrite, and thediazo suspension is coupled with 23 parts oflaphenyl-5-pyrazolone-3-carboxylic acidmethylamide which is dissolved in150 partsv of water with an excess of ammonia. After stirring forseveral hours at 1Q-15" C., the dyestufi which has, precipitated isisolated. In the dry statathe dyestufi is a brown-red powder whichdissolves inconcentrated sulphuric acid and in dilute caustic sodasolution; with a yellowish-red color.

Wool is dyed thereby yellowish redby, afterchroming or by the neutralmetachrome process. The dyeings possess outstanding fastness to light,

Example 6 27.8- parts of, 2, amino-1-hydroxybenzene-5- sulphonic acid-3methylanilide are indirectly diazotize'd in the usual manner with 6.9parts of sodium nitrite, and the diazo suspension is coupled with 21parts of l-phenyl5-pyrazolpne- 3.-carboxylic acid amide which isdissolved, in

100 parts of water with an excess of ammonia. After stirring for severalhours at 10-15 C., the dyestufi which has precipitated is isolated. Inthe dry state the dyestuif, which corresponds to the formula s. l N

is a brown redpowderwhich dissolves in concentrated sulphuric acid andin dilute caustic soda solution with a yellowish-red color.

Wool is dyed thereby full bluish-red shades by after-chror'ning or bythe neutral metachrome process. The dyeings possess outstanding fastnessto light, very good 'fastness to carbonizing and good wet fastne'ss'es.

Further examples with data of the dyeing properties are summarized inthe following table:

Diaz o compon nt Azo component; After-chromel-hydroxy-2aminobenzenei-sulphonic acid-4-chloroanilide jlhydroxy-2-aminobenz ene-5-su1phonicacid-T-chloroanilidel-ljaylroxy-Z-aminobenzene-5-su1phonic acid3-methoxyan- 1 e. a l-ll lyiroxy-2-aminobenzene-5-sulphonicacid-4-mcthoxyane. l-hydroxy-2-amin0-4-chlor0benzene-5-sulphonic acidanilidel-hydroxy-Z-amino-4-methyl-6-sulphonic acid anilidel-hydroxy-Z-amino-S-chlorobenzene-4sulphonic acid anilide1-hydroxy-2amino-fi-methylbenzene--sulphonic acid anilide.

I i- H M H 030mb W N 1-pheny1-5-pyrazolone-3-carboxylic acid amidal-phenyl-5 pyrazo1one-3 carboxylic acid amide.l-pheny1-5-pyrazolone-3-carboxylic acid amide dyeing on wool11hydroxy-2waminobenzene irsulphonic acid anilide 1-(3-chloropheny1) 5pyrazolone-3-carboxylic acid amide yellowish-red.lhydroxy-Z-aminobenzene-5-sulph0nic acidanilide1-(4-methy1phenyl)-5-pyrazolone-3-carboxy1ic acid amide" bluish-red.

yellowish-red.

di nitaries?first: 22s as: sr

1-phenyl-5-pyrazoloiie-ll-carboxylic acid amide Do.

1-phenyl-5-pyrazolone-3 carboxylic acid amidereddish-Borl-pheny1-5-pyrazolone-3}carboxylic acidi l id bl is li r ed.

yellowish-rcd.

very good fastness to ca'rbonizihg and good wet fastnesses.

A dyestufi of similar properties is obtained, if 1-phenyl-5-pyrazolone3-carboxy1ic acid methyl amide is replaced by 1-phenyl-5-pyrazolone-3-carboxylic acid ethyl amide.

Example 5 .The procedure. in each of thesefurther examples is preciselyana ogous to that set forth in the preceding, examples.

Tfi'ejdyle'stuff of the forinu'll:

What we claim is: 1. A new metallizable monoazo dyestufi of the generalformula wherein the group is in one of the unoccupied positionsdesignoted 4, 5 and 6.

2. The new metallizable monoazo dyestufi of the formula O O-NH:

3. The new metallizable monoazo dystuff of the formula 4. The newmetallizable monoazo dyestufif of the formula 5. The new metallizablemonoazo dyestufi of the formula 6. The new metallizable monoazodyestuil' of the formula co-NH. I =N-H0- BIN-0 s Q o= --N/ HANSRUCKSTUHL.

OTTO SENN.

WALTER WEHRLI.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name 7 Date 1,874,474 Eichwede et a1 Aug.30, 1932 2,024,864 Kopp et a1. Dec. 17, 1935

5. THE NEW METALLIZABLE MONOAZO DYESTUFF OF THE FORMULA